Preparation and use of alkylene polyamine sulfenamides and thiosulefnamides



Patented Mar. 9, 1954 PATENT OFFICE "'PREPARATION'-AND USE OF ALKYLENE J POLYAMINE "'SULFENAMIDES AND THIO- SULFENAMIDES I, Chester MuHimel and Le jyille, Okla, ,assignors e 0. Edmonds, Bartlesto Phillips Petroleum Company, a corporation of Delaware 0 Drawing. Application December 28,1948,

.11 .Serial N0..67,768

1 "19 Claims. (0

This inventionrelates tattle-preparation of-orgarlic sulfur polyamidesand .to their uses. In a more particularaspect, thisdnventionrelates to the preparation ofisulfenamides, and .thiosuli'enamides .of alkylene .p c 1yamines, and to lubrieating .oil additives which arezparticularlyyaluableboth in increasingthe stabilityofsa-id oils against oxidative.deterioration and in improving the. corrosion-inhibiting properties ofthe lubricant. In-.,one ,of-.-its,;specific aspectsthe in- 10 .ventionrelates to the pr eparation of .alkylene pol-yamine. sulfenamides; and thiosulfenamides of different,degreesof .substitutionand to they use of these partially substituted; polyamines as lubrieating-oil antioxidantsandcorrosioninhibitors. 15

Many .uses havebeen discovered and developed for.chemical;compounds.,containingszbothsulfur and nitrogen. as-constituents.. oi the compound. Especial-lya-useful are, the compounds-which may be classified .as organic'rsulfurr amides .or more 20, particularly, ;-as sulfenamides e and. thiosulfenamides. Among the numerousmsesto, which they a are applied, thesecompounds.are..-emp1oyed as antioxidants for-lubricatin ;0 il,.. as corrosion-inhibitors forygeneralruse anciasintermediates in ,25 the production :of other usefulicompounds.-;-.Sul-

.-fenamides and; thiosulfenamidesafrom; monoamines have been prepared .by .v-arious, methods,

.. such as the interaction between a, mercaptanand a primary or-secondary-monoamine .andthein- .30

teraction between an: Organic rsulfur halidesand a monoamine. "These interactions; in,the .-.preparation of sulfenamides from-.monoamines :have

been accelerated Jay: the presence of: oxidizin agents, such as the-halogens, .alkaliqhypohali-tes, 35

hydrogen peroxide and the like, and in some instances, in the vpresence-;of;rather weak alkaline solutions. Ina copending applicationz:byrone,of us,- Serial- NO;= 61 7,871;,filedr-Sieptember.72l,.-.19415,

now abandoned; the-:prepa-rationof sulienamides;,40 from a sulfenylhalide -and asmonoamineeunder .deSCI'l'b. ,d'-rann 1;i other copending application by sushi; Serial. -;No.

2,520,400, issued;Aug ust-29, 1 1950, the..preparation-,-. ;45

-01 sulfenamides; rpm a, sulienykhalidetand: a

monoaminepinithe ipresencerof a;. c,lilute -aqueous alkalinezsolution is,=.des ,cribed. ;;;'I h,ese compounds arezespecially usefulqastsl-ubricating ,oil additives gfenyliahalides :in anmannerisimilarsto[then-interactionzoizthe latter;.comnnundsrwithimonoamines11-55 i. 2 and bysuch-interaction, sulfenamides and thiosulfenamides, respectively, may be prepared from polyamines. Furthermore and foremost, we have discovered that the average degree. and extentof substitution-0i the amino groups in the polyamines maybe controlled by suitable adjustment and control of reaction conditions. These compounds arefound tov be highly desirable as additives for oils to prevent corrosion and to retard oxidation .of-the oils. For particular purposes, it is ioundthat the sulfur-, and nitrogen-contain- .ing derivatives of the polyamine compounds-in which only a portion of the amino groupsare substituted with. sulfenyl groups. areespecially desirable. Such compounds have the additional 4. properties .peculiar to sulfenamides while retaining, as aresult ofunsubstituted amino groups, certain chemical characteristics, such as water solubility, which :are afeature of the amines.

When attempts were made to substitute only partially in the amino groups by methods employed with monoamines, We haveiound that only-:rela- .tively minor amounts of .such partiallysubstitutedsulfenamides are formed. When operating in the manner. usually employed with mono- ,amines, substitution appears to, proceedpractieally to completionso that'substantially, allof the possible replaceable hydrogens-of the amino .groups ,are. substituted. 7 However, by. an adjustmentof the concentration. of the alkaline-solution and by other critical factors herein disclosed, it is possible to control effectively thepredominant product of reaction.

According -to the process of our invention wherein the degree of substitution ofthe amino groups-is controlled, the alkylene .polyamine is commingled with aconcentrated. aqueous alkaline solution and then admixed with an organic sulfur halide,such as. a sulfenyl or thiosulfenyl halide, whichtis preferably dissolved in a..low boiling hydrocarbon solvent. The sulfenamide .orthiosulfenamide product or" reaction is. con- -centrated-in the hydrocarbon solvent .phase and mayberecovered by evaporation of., the.solv,ent, preferably under vacuum distillation. Theprod- .1101: of the lighteralkylsulfur halides andlower amines is usually a thick viscous liquid. vItispar- ,ticularly favorable to the reaction that therealso bepresentan. organic .solubilizing. agent,v such ,as chloroform, which-is miscible withthe, hydrocar- -bon and which will increase the solvent powerof hydrocarbon .phase for. the polyamine, the solvent power-ofz-the-aqueous phase for thepolyaminebeing; greatly diminished ,as the concentratiomoi mthe; alkaline-material is, increased.

The exact relative functions of the various components of the reactant mixture in the preparation of the polyamine sulfenamides and thiosulfenamides are not fully understood but a possible explanation is that the alkylene polyamine is transferred from the aqueous alkaline phase to the hydrocarbon phase at such a rate that the substitution of sulfenyl and thiosulfenyl groups on the polyamine molecules takes place according to the normal probability curve; that is, the average degree of substitution will be determined by the ratio of the molecular amounts of sulfenyl or thiosulfenyl halide to the amine equivalents of polyamine employed and thereby to the number of replaceable hydrogens associated with the amino groups. The degree of substitution can be varied at will by increasing or diminishing this ratio. The ratio of sulfenyl or thiosulfenyl halide to the polyamine can be varied in accordance with the degree of substitution desired and with the particular polyamine employed. For example, when using two mols of sulfenyl or thiosulfenyl halide to one mol of an alkylene diamine, the resulting product should be predominantly 50 per cent substituted, while with the same ratio of sulfenyl or thiosulfenyl halide to trialkylene tetramine, the product should be predominantly 33 per cent substituted; in other words, the predominant product will be a sulfenamide or thiosulfenamide in which the substitution is present in a proportion which may be determined from the ratio of mols of reactant sulfenyl or thiosulfenyl halide, respectively, to replaceable hydrogens in the amino groups. In the absence of concentrated alkali and an organic solubilizing agent for the polyamine, substitution proceeds substantially to complete replacement in the molecules which undergo reaction. On the other hand, with concentrated alkaline solutions and a solubilizing agent the control described can be effected.

Alkylene polyamines adaptable to our process compris compounds of the general formula H2NE (CH2) INH11/H in which :1: represents a whole number greater than one, preferably a Whole number of 2 to 6 inclusive, and in which y is a whole number, preferably from 1 to 10. Although a: will probably not be much greater than 6, the value for y may vary over a much wider range, up to 100 or higher. From an examination of the general formula, it is readily observed that the possible number of replaceable hydrogens in the amino groups of the polyamine may be determined by the expression y+3 or in other words, is two more than the number of amino groups in the amine molecule. Typical compounds of this formula are ethylene diamine and its homologues, diethylene triamine, triethylene tetra.- mine, tetraethylene pentamine, dipropylene triamine, butylene diamine, and the like.

The organic sulfur halides employed in this process may be represented by the formula R-Sm-X, in which R represents alkyl, aryl or aralkyl radicals and corresponding substituted radicals; X represents a halogen, preferably chlorine, although iodine and bromin are likewise applicable; and m is an integer 1 or 2. Thus the sulfur halides include the compounds particularly denominated sulfenyl halides and thiosulfenyl halides, the former disclosed and claimed in U. S. Patent 2,123,082, issued July 5, 1938, and the latter disclosed and claimed in the co-pending application, Serial No. 89,475, filed April 25, 1949. These reactant halides can be obtained from any convenient source or can be prepared as used, if desired. For example, as disclosed and, claimed in the said co-pending application Serial No. 89,475, they can be prepared by the interaction of a corresponding mercaptan or disulfide with elemental halogen and preferably in the presence of an organic solvent. It is particularly advantageous to employ as a solvent in the preparation of the sulfenyl halide or thicsulfenyl halide reactant, a hydrocarbon which may also be used as the solvent in the reaction forming the corresponding sulfenamide or thiosulfenamide. In such a case the reactant halide as formed in the hydrocarbon may be used directly in the preparation of sulfenamides or thiosulfenamides without separation from its solvent. This is a particularly desirable manner of operation in the case of those organic sulfur halides which are unstable and tend to decompose during separation from the solvent in which they are prepared.

The alkaline material employed in the practice of the present invention is preferably sodium hydroxide which is preferred because of its cheapness and ready availablity. However, the process of the present invention can be practiced with the hydroxides and carbonates of alkali metals, such as sodium, potassium or lithium and with the oxides, hydroxides and carbonates of other metals, such as calcium and other alkaline earth metals, which furnish an aqueous alkaline solution of the desired concentration. For control of the degree of substitution of the amino groups of the polyamine, the concentration of the alkaline aqueous solution can be varied within the range between 35 per cent by weight and per cent by weight, depending upon the relative concentrations of the reactants and upon the degree of substitution desired. When substituting the polyamine molecules only partially, relatively large amounts of highly concentrated alkaline solution is used and the amount of alkaline material to be used may be related to the sulfenyl or thiosulfenyl halide employed. For example, when employing the preferred sodium hydroxide, the molar ratio of caustic to sulfenyl or thiosulfenyl halide may be in the range of 1.0 to 5.0, preferably within a range of 1.2 to 2.0.

The solubilizing agents employed in the present process comprise organic materials which are miscible with the hydrocarbon solvent in which the sulfenyl halide is dissolved and which possess a high solvent power for the alkylene polyamine employed. It is necessary that the solubilizing agents be inert with respect to the reactants, as well as to the alkaline material and the solvent employed in the respective phases. Suitable solubilizing agents include chloroform, carbon tetrachloride, dioxane, and ethers, such as diethyl and dipropyl ethers and their halogenated derivatives. It has been found that chloroform is especially adaptable and available as a preferred solubilizing agent.

The solvent employed for the sulfenyl halide or thiosulfenyl halide will preferably be a paraffin hydrocarbon, such as pentane or hexane, or a mixture of such hydrocarbons. It is particularly efficacious to employ'a mixture which boils at the desired reaction temperature so that the reaction may be carried out in the presence Of refluxing solvent. By operating in the presence of such a refluxing solvent, reaction temperatures can be easily maintained at the desired level and a certain degree of agitation is automatically provided. It is essential that the solvents selectcedcberfizeezfrom appreciableizamountsmf isulfur,

centration 'rof :sulfenyl; or? thios-ulfenyl halide in wthe: solvent does not appear :tobe vcriticaLf' ut i "-is satisfactory toiopera-te-in the concentration range where one gram mol of the organic sulfur halide reactant is dissolved in 800-1600 cc. of solvent.

"The reaction proceeds smoothly at atmospheric jpressure and room'temperature." However, where desirable, pressures either above or below atmosphericmay" be employed. Likewise, a"tempera "ture' within the range betweenO" and 65 C.,"b'ut preferably between 20 I'and:35.' C., may be employed, although a temperature" beyond these 1 limits either way may also be used, depending upon thestability ofthe reactants andthe products. Although it'is possible to 'add all the reactants initially in conducting'the process, control of the temperature and of the reaction is more diflicult. Hence a preferred method is to dissolve the amine in the solubilizing agentthe chlro-, form for example, and. then thoroughly admix the aqueous alkalinesolution.therewith. The organic sulfur halide reactant should be separately dissolved in a suitable hydrocarbon solvent. and

"this solution added'slowly with constant agitation to the alkaline solution of the polyamine;

as suggested above; the sulfenyl or thiosulfenyl halide may conveniently be prepared in the presenceof a hydrocarbon solvent which will be satisfactoryfor the present reaction and therebythe hydrocarbon solution of :organic sulfur halide reactant will be' ready foruse as soon as prepared. Upon mixing the respective solutions of halide reactant and th alkylene polyamine,

reaction proceeds smoothly with vthe formation go --of the desired sulfenamide 'or "thi'osulfenamide and by-producthydrogenha'lidej the sulfenamide or thiosu-lfenamide product is concentrated 1 oil additives and are particularly effective as antioxidants. Particularly beneficial improvements have been found when small amounts of the sulfenamides are employed.

Thesecompounds, when added in relatively small quantities 'to. lu-

: bricating oils, 'favorably inhibit the "tendencyrof the oils to oxidize and; at the same time, do not produce deleterious eiiects .on other properties. The amount of the N-sulfenyl polyamides emrployedwill usually be less than 8 .per cent by *weight'based on the weight 'of'the oil andgeneral- 1y it will range between 0.01 and per cent by weight. Is is found that additions of these, poly- "amides ,enhance'the anti-corrosive properties of 'the'oils in engine performance.

Upon heating in "the presence'of oxygen, most 'uninhibited'oils show marked increases. inthe.

values'for neutralization numberand viscosity.

These values may be considered as indicationsof the stability "of a 'givenoil toward, oxidation and "there is generally a'fdirect correlation between antioxidant efiectand these values. Inmost oils Janincrease in viscosity occurs, oniheatingin air .and an antioxidantprevents or reduces, thisin- ...crease.

Oxidation stability of .boththe unin- M hibited .and inhibited vbils wasldetermined by' the Government test whielnisflesignated as: Federal Specification Well-791b, Method.34 5.2- Stabil- ""ity "ofi'LubricatingfOils. fThisiis.-. a'" 'welleknown and accepted"method'tfordeterminingflubricat- 5 ing oil stability'dni which taredsamplespffthe oiltare'heatedin 'contactwitlrairjat at constant temperature f'of 350"Efor twenty=four hours and. l the" changes inf'physical characteristics resulting ".fromthe heatingare determined. Y 10 1 The corrosionei'nhibiting properties fof a "lubri- "eating oil are detemin'edrfroni theweightfloss' fof '.:tared test; connecting=rod bearings. a standard'test denominated "by the Society 'oflA'utomo- .tive Engineersas "the Lauson EngineffTestfPro- 5 .cedurev BLT-1A; a determiriatiomis'madejof the "bearing loss in"milli'grams""of 'weightduringiop- 'er'ati'on'of a Lauson engine 'at'c'onstantspeedand ""load' for a'totaliofi60' hours i for "SAE "1 01 grade'foil and 80'. hours for heavier grade' oils while mainzytaining the'test-oil'inthe engine-at a rgiventemperature. V

"The following exanipl'es illustrate?theresults and 'degrees'of substitution which may; beg'obtained by control of the ratioofreactants andthe .5 presence of concentratedral-kaline solution in the preparation, of various. sulienamides. Certain of jthe'- examples .alsoishoW'S the yaluetof lthegpoly- .amidesas' ,lubricatingbil. additiVeSQinQI'IIhibiting oxidation and corrosion.

Example 1 Comparative experiments werem'onducted in r the preparation of-lii-siilfenylderivatives--of-tetra- -1 =ethylene pentamines.

? In the first-experiment l A) one =mo1 'of tertiary-butylsulfenylchlol idein 1600 "coi oi dsopentane was mix(Ed -with 0.5 moi ofitetraethylene I pentamine -in 240 *grams ofizu per cent aqueous solution of sodium hydroxide. The mixture was stirred vigorously at the temperature of refluxing isopentane for one-hour.

In asecond experiment ""(run -B) "the" same amounts of reaction materialswere employed but the pentamine-was dissolved "in-400 "grams 'of' a per cent sodium hydroxide solution and solubilized in the non-aqueous phase with 400 cc. oi. chloroform as the solubilizing agent. The mixture was stirred vigorously while the tertiarybutyl sulfenyl chloride in isopentane was added; H0 stirring of the mixture was continued for one hourin the refluxing isopentane.

In :each case the product was isolated by separating the non-aqueous layer and removing the solvent therefrom by vacuum distillation. The resulting viscous liquid product was then washed with distilled water and dried. The percentage yield basedon the sulfenyl chloride added and the percentage nitrogen 'Lin" theiamide product were determined." Theaverage-degree of substitution was computed onthe'basisofequivalents of hydrogenrepla'cediby sulfenyl groupsandthe percenta'geof substitution was computed on thebasis of the "ratio of equivalent "hydrogens replaced jto the :total" irplacea'blehydrogens 'in the amino .65 groups.

""I'he'results-of the twoexperiments' arerecord'ed below.

. Substitution Sulfenamide "Nitrogen T --Run IiYie Gont'ent (percent) v. mercent) Average Average Degree Percent A '78 I 9.64 6.1 f 87.3

- Example 2 1.1 mols of tetraethylene pentamine were added to liters of chloroform. To this'mixture was added 400 grams of a 50 per cent aqueous solution of sodium hydroxide (5 mols of sodium hydroxide) While the mixture wasstirred vigorously, a solution of 5 mols of tertiary-butyl sulfenyl chloride in 8 liters of n-hexane was added gradually. The tertiary-butyl sulfenyl chloride was previously prepared in the hexane by passing chlorine into the hydrocarbon solution of ter- Example 3 2.0 mols of tetraethylene pentamine were dissolved in 5 liters of chloroform and admixed with 400 grams of a 50 per cent aqueous solution (5 mols) of sodium hydroxide. To this mixture was slowly added 4. mols of tertiary-butyl sulfenyl halide in solution in 6 liters of pentane. The reaction mixture was stirred for approximately one hour at a reaction temperature of approximately 35 to 45 C. The product was isolated as above and had an average degree of substitution of 3.0. The yield based on the sulfenyl halide was 85 per cent. The average per cent of substitution was 43.

Example 4 2.0 mols of tetraethylene pentamine were dissolved in 5 liters of chloroform and admixed with 400 grams of a 50 per cent aqueous solution of sodium hydroxide (5 mols of sodium hydroxide).

8 when using the oil containing 1.5 per cent of the tetraethylene pentamine penta-tertiary-butyl sulfenamide, bearing loss was 85 per cent less than when using the untreated oil, specific values being a loss of 870 mg. with the untreated oil and 136 mg. with the oil containing the additive. These data were obtained in an 80-hour Lauson engine test at a crank case temperature of 285 F.

Eznample 6 The partially substituted sulfenamide, that is, tetraethylene pentamine tri-tertiary-butyl sulfenamide, prepared in Example 3, was tested as a bearing corrosion inhibitor in a commercial SAE 30 lubricating oil. The sulfenamide was added to the lubricating oil in a concentration of 2.5 per cent. Results of this Lauson engine test show that bearing corrosion was reduced by 89 per cent when using this sulfenamide additive. Specific values obtained are tabulated below.

Bearing None 2.5

Example 7 Samples of the tetraethylene pentamine pentatertiary-butyl sulfenamide from Example 2 hereinafter referred to as additive A, and the tetraethylene pentamine tri-tertiary-butyl sulfenamide from Example 3 hereinafter referred to as additive B, were tested to determine their antioxidant properties. These additives were mixed with a neutral oil and the blends heated by the aluminum block method as specified in the test Federal Specification VV-L-791b, Method 345.2. Properties of the treated oils were studied and compared with the properties of a control test carried out on a sample of the oil in which no additive was used. Results of these tests are tabulated below:

Oil 1.0 Oil 1.0 Control percent A percent B Heated Heated Heated New New New at 350 at 350 at 350 011 F. 0.1 F. 011

Neutralization Number 0. 00 0. l3 0. 01 0. 05 0. 00 0. O6 V scosity at 100 F. (SUS) 476. 4 499. 6 477. 8 493. 6 477. 3 494.1 Viscosity at 100 F. (SUS) (corrected 492. 7 493. 6 493.1 Viscosity Increase, percent 1.4 0.0 0.2

1 Viscosity of unheated oil corrected for evaporation loss.

Example 5 A portion of the tetraethylene pentamine penta-tertiary-butyl sulfenamide of Example 2 was added to a commercial SAE 30 lubricating oil in a concentration of 1.5 per cent by weight. Lauson engine corrosion tests were run on the oil with parallel tests being run on untreated oil as a control.

Results of these tests show that From the foregoing examples it can be seen that the N-substitution of the polyamines may be controlled to prepare sulfenyl derivatives of the desired degree of substitution, which are useful as lubricating oil anti-oxidants and corrosion inhibitors. The experiments of Example 1 clearly illustrate by comparative results the control of substitution to be effected by the concentration of the alkaline solution and use of solubilizing agents. It is shown that, under the same conditions except alkaline concentration and solubilizing agent, substitution proceeds substantially to completion when weaker alkaline solution is employed, while the degree of substitution is substantially equivalent to the molecular ratio of sulfenyl halide to polyamine when the alkaline solution is concentrated. A comparison of the results and of the product in each of Examplesl, 2'and 3 shows further that the degree of substiam nes;

tutionrisaa v.functioniofatheiratioiofthe. reactant when ,reaction :is: efiected lin zpresence of. concen-v trated-alkaline solution; Asthe ratio. of sulfenyl;

halide is increased withsrespect .to the. amine in theepresence .oi the. same concentrated alkaline solution:.and under the-same .conditionsp the degree of) substitution. is also increased. Thus the;

degree of substitutionzmay be; altered .by. employing-concentrated alkaline solution as; solvent for: the polyamine insteadbf weak'alkaline solution;

and, :when so employing the concentrated; alkalinesolution, varying degrees-bf:partial. substitution may beeifected. In.other-wordsgzsulfenyl.

polyamides may be :preparedby. reaction f 'su1.-' fenyl halideswith polyamines in-the absence of or-- in the presence of aqueousalkalineisolutions, but -inthe case of-weak' alkaline solutions, reaction may not be controlled.and-substitution will be substantially .completcon the polyamine reacting; whereas, in thecase :of concentrated alkalinesolutions, the degreeof substitution may be-controlledbyvarying the ratio. of .the sulfenyl halide to the amine for any particular. polyamine.

Examples 4, 5, and-'6 amply-showthebenefits and; improvements -which areobtained by .the

c-oneisting'of chlorine, bromine, and iodinaand m is an integer selected from; the group .consist ing-of. 1 and 2,, a normallydiquid; hydrocarbon as asolvent for said halide, anzaqueous inorganic alkalineagent in, an amount-to provide said alkaline agent in a mol ratio tosaidhalide in the range of from 1.011 to 5.011 and containing said alkaline agent in a concentration of from 35-70 weight per cent, andanorganic liquid chemically inert t0 the components bfthe-resulting admixture and capable of increasing the solvent power of said hydrocarbon liquid for" said g-polyamine and selectedfromthe group -consisting-ofachlorinated hydrocarbon, dioxane, an ether, and a halogenated derivative of said ether; maintaining said admixture at a temperature within the limits of 20 and 65 (3., whereby only a portion of the replaceable Hs associated with the amine groups of the reactant amine are substituted by a sulfenyl radical; and the degree of the partial substitution. thus obtained is variable, directly with said ratio of halide to polyamine, inversely with the concentration of alkaline agent in the said 3540 per cent range and inversely with the ratio of said alkaline agent to said halide in the said range of 1.011 to 5.0:1; and recovering from sulfenyl chloride dissolved -ina.hydrotiarbon-- 103 the resultin ;1'e Qti n mixtur lfenamide product of said partial substitution.

2.; A process comprising introducingtert-butylthiosulfenyl chloride dissolved in a hydrocarbon solvent into admixture with tetraethylene pentamine in-a ratio of molsof said-chloriderper -molr of said pentamine lessthan the numberofram ne; equivalents of said .pentamine, an. aqueous alkali metal hydroxide solution in,-an;amount to pro-- vide said hydroxide in a mol ratioto said-halide; in the rangeoffrorn 1.0:1 to 5.0:1 andcontain ing/said hydroxide in a concentration ofdroid;- 35-70 weight per cent, and with chloroformas a solubilizer to increase the solvent power ;of,sai,d

' hydrocarbon iorsaid pentamine maintaining the:

resulting admixture at 0-"65 c whereby only a portion ofthe replaceable Hs associated :jWitlLp the amine groups of :said pentamine reactant-are substituted by .a tert-butylthiosulfenyl radical and the degree of the partial substitution it obtained, is variable, directly with -said ratio of chlorideyto saidpentamine, inversely with the concentration of hydroxide, in said concentratio range and inversely with the ratio 'of said;hy droxideto said halide inthe said range of; 3 2' to 5.011, and recovering from the resulting re action mixture *2. sulfenamide productgof; said partial substitution.

3. A'process comprising, introducing tert-butyl solvent. into admixture with tetraethylenerpe amine in a ratio of mole of saidhhloriderper mo 4, 3 of said pentamine less. thanthe, number Of! amin equivalents of said pentamine, an aqueous alkali metal hydroxide solutionin anamounttoprovid r said hydroxide. ,in a mol= ratio :to-said. halida n;;. the range of from 1.0:1 to 5.011 andcontaining said hydroxide in a concentration;of' fromz35e7o weight per cent,. and with chloroform as. a solubilizer to increase the solvent power. of. said by,

drocarbon for said-pentamine; maintaining-the;

resulting admixture at 0-65."; 0.; whereby .only a portion of the replaceableHs'associateduwiththe raminegroups of said pentamine reactant, 8,118:

' substituted byv .a tert-butylsulfenyl; radicals and;

the-degree-of the partial substitution thus; ob: tained is variable, directly with:;saidzratiorofchloride-to. said pentamine, inversely with the concentration of hydroxidezin said concentration; rangeand inversely Withatheratio-of. said hydroxide to said halide in the said rangeof- 1.0;;1; to 50:1,. and recovering.from,the.resulting.reaction mixture a .1 sulfenamide product :of saide partial substitution 4. The process of claim zpwhereinisaid rent-1 amine is... dissolved. in said. solubilizer and said aqueous alkaline solution is then admixed "Withx the solution of pentamine-solubilizer. so. formed, and" wherein: said I hydrocarbonesulfenyl I halide solution is then added with agitation ,during -av predetermined: period: -'0f-. time to theiresulting solution. of solubilizer, sulfenyl halidepandjaqueous alkaline solutionso formed;

5. The process of. claim-.3 zwherein. saiclpentaa *mine is dissolvedrin said-solubilimr and said concentration of alkaline agent is at least 50 weight per cent, and wherein said mol ratio of alkaline agent to sulfenyl halide is within the limits of 1.221 and 2:1.

7. The process of claim 1 wherein said polyamine is dissolved in said solubilizing agent, wherein said aqueous alkaline agent is admixed with the resulting solution of polyamine and solubilizer, and a sulfenyl halide-hydrocarbon solution is then added with agitation over a predetermined time duration to the resulting solution of solubilizer, polyamine, and alkaline material.

8. The process of claim 1 wherein said sulfenyl halide is prepared in a hydrocarbon solvent by reacting a halogen with an organic compound selected from the group consisting of a mercaptan and a disulfide, and the resulting reaction product solution is applied as said sulfenyl halidehydrocarbon components.

9. The process of claim 1 wherein said polyamine is an alkylene diamine and wherein two mols of said halide per mol of said diamine are introduced into said resulting admixture, and wherein a corresponding sulfenamide is produced, predominantly 50 per cent substituted.

10. The process of claim 1 wherein said polyamine is an alkylene triamine and wherein two mols of said halide per mol of said triamine are introduced into said resulting admixture, and wherein a corresponding sulfenamide product is formed, predominantly 33 per cent substituted.

11, The process of claim 2 wherein said hydrocarbon solvent is isopentane, said alkaline material is sodium hydroxide, said reaction is conducted in the presence of refluxing isopentan'e, and said sodium hydroxide concentration is at least 50 weight per cent.

12. The process of claim 2 wherein said pentamine is dissolved in said solubilizer and said aqueous hydroxide solution is then admixed with the solution of pentamine-solubilizer so formed, and wherein an isopentane-sulfenyl halide solution is then added with agitation during a predetermined period of time to the resulting solution of solubilizer, sulfenyl halide and aqueous alkaline solution.

13. The process of claim 1 wherein said sulfenyl halide is tert-butylthiosulfenyl chloride.

14. The process of claim 1 wherein said sulfenyl halide is tert-butylsulfenyl chloride.

15. The process of claim 1 wherein said polyamine is tetraethylene pentamine.

16. The process of claim 1 wherein y is an integer of from 1 to 10.

17. The process of claim 1 wherein said solubilizer is chloroform.

18. The process of claim 1 wherein said aqueous alkaline agent is an aqueous alkali metal hydroxide.

19. 'A process for the interreaction of an alkylene polyamine with a sulfenyl halide to form a sulfenamide, comprising admixing an alkylene polyamine characterized by the formula HzNE (CH2) xNH] 1H 12 wherein a: is an integer greater than 1 and y is an integer equal to at least 1, with an organic halide in a ratio of mols of said halide per mol of said polyamine less than the number of amine equivalents of said polyamine, said halide being selected from the group consisting of an alkyl sulfenyl halide and an alkyl thiosulfenyl halide, a normally liquid hydrocarbon as a solvent for said halide, an aqueous inorganic alkaline agent in an amount to provide said alkaline agent in a mol ratio to said halide in the range of from 1.011 to 5.0:1 and containing said alkaline agent in a concentration of from 35-70 weight per cent, and an organic liquid chemically inert to the components of the resulting admixture and capable of increasing the solvent power of said hydrocarbon liquid for said polyamine and selected from the group consisting of a chlorinated hydrocarbon, dioxane, an ether, and a halogenated derivative of said ether; maintaining said admixture at a temperature Within the limits of 20 and 65 0., whereby only a portion of the replaceable Hs associated with the amine groups of the reactant amine are substituted by a sulfenyl radical and the degree of the partial substitution thus obtained is variable, directly with said ratio of halide to polyamine, inversely with the concentration of alkaline agent in the said 35-70 per cent range and inversely with the ratio of said alkaline agent to said halide in the said range of 1.0:1 to 5.0:1; and recovering from the resulting reaction mixture a sulfenamide product of said partial substitution.

CHESTER M. HIMEL.

LEE 0. EDMONDS.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date Re. 19,286 Zaucker et al Aug. 21, 1934 1,832,328 Scott Nov. 17, 1931 2,123,082 Schulze July 5, 1938 2,244,075 Mikeska June 3, 1941 2,268,467 Ashworth Dec. 30, 1941 2,271,834 Carr Feb. 3, 1942 2,333,468 Cooper Nov. 2, 1943 2,343,538 Ebelke Mar. 7, 1944 2,404,695 Coleman July 23, 1946 2,439,734 I-Iimel et a1. Apr. 13, 1948 2,460,393 Paul Feb. 1, 1949 2,476,655 Fox et a1 July 19, 1949 2,520,400 Himel et a1 Aug. 29, 1950 2,520,401 Himel et a1 Aug. 29, 1950 2,554,097 Edmonds May 22, 1951 FOREIGN PATENTS Number Country Date 551,207 Great Britain Feb. 11, 1943 OTHER REFERENCES Rheinholdt et a1.: Ber. Deut. Chem., vol. 72 (1939) pp- 659, 664 and 665, 669 and 670. 

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